Enantio- and Regioconvergent Nickel-Catalyzed C(sp3)−C(sp3) Cross-Coupling of Allylic Electrophiles Steered by a Silyl Group

Abstract

A two-step sequence for the enantio- and diastereoselective synthesis of exclusively alkyl-substituted acyclic allylic systems with a stereocenter in the allylic position is reported. The asymmetric induction and the site selectivity are controlled in an enantio- and regioconvergent nickel-catalyzed C(sp3)−C(sp3) cross-coupling of regioisomeric mixtures of racemic α-/γ-silylated allylic halides and primary alkylzinc reagents. The silyl group steers the allylic displacement towards the formation of the vinylsilane regioisomer, and the resulting C(sp2)−Si bond serves as a linchpin for the installation of various C(sp3) substituents in a subsequent step.